EP3141565A1 - Particules sphériques - Google Patents

Particules sphériques Download PDF

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Publication number
EP3141565A1
EP3141565A1 EP16188726.0A EP16188726A EP3141565A1 EP 3141565 A1 EP3141565 A1 EP 3141565A1 EP 16188726 A EP16188726 A EP 16188726A EP 3141565 A1 EP3141565 A1 EP 3141565A1
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EP
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Prior art keywords
magnesium
halogen
spherical particles
mixture
boiling point
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EP16188726.0A
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German (de)
English (en)
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EP3141565B1 (fr
Inventor
Michael GRÜN
Klaus Heyne
Claudine Mollenkopf
Sam Lee
Roger Uhrhammer
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Ineos Europe AG
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Evonik Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/28—Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/50—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from alkaline earth metals, zinc, cadmium, mercury, copper or silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size

Definitions

  • the invention relates to spherical particles comprising magnesium alcoholates or a mixture of magnesium alcoholates, a process for their preparation and their use.
  • US 5965478 (date of application : 13/08/1997, Toho Titanium) describes a magnesium ethanolate having a bulk density of 0.25 - 0.40 g/ml and a particle diameter of 1 to 100 ⁇ m as a component of a Ziegler-Natta catalyst. This is prepared by continuous or batchwise addition of alcohol and magnesium to a reaction mixture which is not defined in more detail. The synthesis takes place at the reflux temperature.
  • the flowability of the powder is of great importance for the processing and handling of pulverulent substances.
  • a rapid flowing out of the magnesium alcoholate powder saves time and expenditure.
  • a good flowability of the magnesium alcoholate powder must also be ensured because this class of substance is highly sensitive to air and water. Residues of substance in drums which have not been emptied completely are a high safety risk. Due to the good flowability, there is also a reduced risk of bridge formation when transferring to silos. Pneumatic delivery of the powder is also facilitated.
  • the object of the invention is to prepare spherical particles comprising magnesium alcoholate or mixtures of magnesium alcoholates having a good flowability. These particles can serve, for example, as starting substance (catalyst precursor) for olefin polymerization catalysts.
  • the invention provides spherical particles comprising magnesium alcoholates or mixtures of magnesium alcoholates, which are characterized in that they have a poured cone height of less than 17 mm.
  • Measurement of the poured cone height under precisely defined conditions is a measure of the flowability of a pulverulent substance.
  • the angle of repose is a further evaluation criterion for the flow properties. Since given the same base dimension the poured cone height depends directly on the angle of repose and is considerably easier to determine, this is determined.
  • Another method for determination of the flowability of powders is, for example, measurement of the discharge speed using a modified Pfrengle discharge funnel [DIN ISO 4324].
  • the invention also provides a process for the preparation of the spherical particles comprising magnesium alcoholates or mixtures of magnesium alcoholates according to the invention, which is characterized in that magnesium, an alcohol or a mixture of various alcohols and a halogen and/or a halogen compound are reacted with one another at below the boiling point of the alcohol component having the lowest boiling point, and the product obtained is separated off and dried.
  • the alcohol component having the lowest boiling point can have a boiling point of 68 °C. It can be, for example, methanol.
  • the main constituent of the spherical particles according to the invention can in general be magnesium ethanolate.
  • the content of the other magnesium alcoholates (in addition to magnesium ethanolate) and of a halogen-containing constituent present can be between 0.001 wt.% and 15 wt.% (in each case based on the total weight).
  • Particularly preferred spherical particles are those for which a mixture of ethanol, methanol and isopropanol is employed as the alcohol mixture in the preparation and the contents of the alcoholates in the end product are as follows:
  • the spherical particles can comprise small amounts of free alcohols and furthermore Mg(OH) 2 and/or MgCO 3 .
  • the magnesium can be employed in the form of strip, filings, granules or also powder. Magnesium which is not coated or coated only with a thin oxide/hydroxide layer is preferred.
  • Mono- and polyhydric alcohols which have a linear or branched carbon chain can be employed as alcohols for the synthesis.
  • the alcohols can be aliphatic, aromatic or mixed aliphatic-aromatic. Alcohols having 1-10 carbon atoms are preferably employed.
  • Ethanol is particularly preferred as the alcohol. If an alcohol mixture is employed, ethanol can be employed as the main constituent and methanol and isopropanol as secondary constituents.
  • the mixture of the alcohols can consist of
  • the molar ratio of the alcohol or alcohol mixture (calculated as the sum of the moles of the individual constituents of the alcohol mixture) to magnesium can be between 1 and 100. It can be particularly preferably between 3 and 20.
  • a non-limiting selection for the halogen or the halogen-containing component is:
  • Magnesium alkoxyhalides such as, for example, magnesium ethoxyiodide, magnesium methoxyiodide, magnesium isopropoxyiodide, hydrogen chloride, chloroacetyl chloride and organic acid halides such as benzoyl chloride, phthaloyl chloride, acetyl chloride, propionyl chloride, butyryl chloride, trimethylacetyl chloride, trifluoroacetyl chloride, and chloroacetyl chloride.
  • organic acid halides such as benzoyl chloride, phthaloyl chloride, acetyl chloride, propionyl chloride, butyryl chloride, trimethylacetyl chloride, trifluoroacetyl chloride, and chloroacetyl chloride.
  • the halogen compound can be an organic acid chloride.
  • the acid chloride can be a chloroacetyl chloride.
  • Chloroacetyl chloride, iodine, magnesium iodide and magnesium chloride as well as magnesium alkoxyhalides are particularly preferred.
  • halogens or halogen-containing substances can be employed in the reaction both in the pure state and in the form of solutions.
  • the halogen or the halogen-containing components can also be present in a chemically modified form after the reaction.
  • iodine can be present partly as magnesium iodide and/or magnesium alkoxyiodide.
  • the reaction can be carried out at a reaction temperature of between 0 °C and 67 °C, it also being possible for the reaction temperature to be changed during the reaction.
  • the particle size can be determined by the choice of the reaction temperature.
  • the pressure can be between 0.001 and 100 bar.
  • the reaction can preferably be carried out under atmospheric pressure.
  • the sequence of the addition of the reaction partners can be as desired. The following reaction procedure is particularly preferred:
  • the end of the reaction can be recognized by the evolution of hydrogen stopping.
  • the reaction time can in general be 5-50 h.
  • the product can be washed again, for example with the alcohol mixture used for the preparation, in order to adjust the content of halogen or halogen-containing component.
  • the molar ratio of the halogen or halogen component to magnesium at the start of the reaction can be between 0.0001 and 0.5. In the end product, it can be between 0.000001 and 0.5.
  • the average particle diameter (d 50 ) of the spherical particles according to the invention can be between 1 and 200 ⁇ m.
  • the particle diameter is particularly preferably between 10 and 50 ⁇ m.
  • the form of the particles can preferably be spherical.
  • the specific surface area can be between 2 and 100 m 2 /g.
  • the specific pore volume is between 0.01 ml/g and 4 ml/g.
  • the bulk density can be at least 0.25 g/cm 3 .
  • the tapped density can be at least 0.35 g/cm 3 .
  • the spherical particles according to the invention can be employed as a precursor for olefin polymerization catalysts, thus, for example, as a catalyst support precursor.
  • the specific surface area is determined by nitrogen absorption at 77 K in accordance with DIN 66131 (calculation according to the BET model).
  • the specific pore volume is measured by mercury intrusion to 2,000 bar in accordance with DIN 66133.
  • the particle size distribution is measured with a Microtrac-X100 apparatus from Microtrac in accordance with the principle of laser diffraction using unified scatter technique.
  • the apparatus is equipped with one primary (on-axis) laser diode and two secondary (off-axis) laser diodes with one forward and one high-angle photo detector array. The range is 0.04-704 micron.
  • the sample is suspended in ethanol before the measurement. Ultrasound was applied for 60 seconds before measurement.
  • a Horiba LA-920 was used.
  • the samples were suspended in isopropanol and subjected to ultrasound for 60 seconds.
  • a circulation speed of 7 was used before measurement.
  • the bulk density and the tapped density are determined as follows:
  • a given volume of the powder is poured through a funnel into a measuring beaker and its weight is determined.
  • a given volume of the powder is poured through a funnel into a measuring beaker and vibrated and its weight is determined.
  • the measuring beaker is tared on a balance and covered with a sheet of paper. Thereafter, the filling funnel is placed on the paper. A sample of approx. 150 cm 3 is loosely introduced into the filling funnel. The paper is then removed, so that the sample falls into the measuring beaker. If necessary, the flow of the sample can be assisted by stirring with a rod (or spatula).
  • the powder mass piled up above the upper edge of the measuring beaker is skimmed off with a straight-edged blade or ruler at an angle of 45° with respect to the piled-up powder mass.
  • the measuring beaker filled with the powder is weighed to 0.1 g and the weight (weight of magnesium alcoholate powder) is recorded.
  • the arithmetic mean - in addition to the individual values - of the two determinations is to be stated as the result of the test.
  • the measuring beaker is tared on a balance and covered with a sheet of paper. Thereafter, the filling funnel is placed on the paper. A sample of approx. 150 cm 3 is loosely introduced into the filling funnel. The sheet of paper is then removed, so that the sample falls into the measuring beaker. If necessary, the flow of the sample can be assisted by stirring with a rod (or spatula). Thereafter, the contents of the measuring beaker are vibrated (measuring beaker vibrated and tamped) until the powder cannot be compressed further. During this operation, the measuring beaker is constantly topped up with sample material.
  • the powder mass piled up above the upper edge of the measuring beaker is skimmed off with a straight-edged blade or ruler at an angle of 45° with respect to the piled-up powder mass.
  • the measuring beaker filled with the powder is weighed to 0.1 g and the weight (weight of magnesium alcoholate powder) is recorded.
  • the arithmetic mean - in addition to the individual values - of the two determinations is to be stated as the result of the test.
  • the alcoholate contents in the end products are determined by hydrolysis of the alcoholate mixtures with acid. After neutralization, the alcohols released are determined by gas chromatography (HP 5890 gas chromatograph with DB 624 as the stationary phase, 2-butanol as the internal standard).
  • the halogen content is determined by potentiometric titration after hydrolysis of the sample with ethanol/acetic acid (Metrohm Titroprocessor 682, indicator electrode: silver rod, reference electrode Ag/AgCl/0.1 M HClO 4 )
  • the poured cone height is determined as follows:
  • the wire sieve is fixed to the stand approx. 10 cm above the metal solid cylinder.
  • the powder is poured slowly on to the sieve and carefully passed through the sieve by means of the scraper.
  • the distance from the sieve to the poured cone tip of the powder is then adjusted to 2 cm.
  • sieving of the powder is ended and the poured cone height is read off at the tip of the cone with the surface gauge.
  • Figure 1 shows a diagram of the poured cone height measurement.
  • the poured cone height is stated in mm.
  • the reading error of the poured cone height is 0.1 mm.
  • the average deviation of repeated measurements on a sample is 0.2 mm.
  • Example 1 Example 2 Example 3 Example 4 Magnesium [g] 145.0 105.0 145.0 145.0 Iodine [g] 10.78 15.68 10.78 10.78 Alcohol mixture [g] 1549.5 1549.5 1549.5 Wt.% (EtOH) 91.2 89.5 91.2 91.2 Wt.% (MeOH) 3.5 5.2 3.5 3.5 Wt.% (i-PrOH) 5.3 5.3 5.3 Wt.% (iodine) based on magnesium 7.5 14.8 7.4 7.4 Reaction temperature [°C] 50 50 50 50 d 10 [ ⁇ m] 3.8 12.2 21.5 4.0 d 50 [ ⁇ m] 18.6 25.0 30.5 22.7 d 90 [ ⁇ m] 25.5 35.9 43.2 30.7 Span 0.71 0.95 0.71 1.18 Bulk density [g/ml] 0.43 0.39 0.44 0.42 Tapped density [g/ml] 0.54 0.49 0.58 0.55 Poured cone height [mm] 12.5 13.3 15.6 13.4 methanol after hydrolysis [w
  • a 2-L Buchi glass reactor is equipped with an overhead stirrer with a paddle-type agitator on the bottom of the shaft and a U-shaped agitator staggered directly above the paddle.
  • the reactor is charged with absolute ethanol (930 mL, 99.5 %, Aldrich), magnesium turnings (40 g), then chloroacetyl chloride (10.0 mL), all under a nitrogen blanket.
  • the stirrer is set to 200 rpm and the reaction is allowed to proceed without temperature control. After 63 hours of stirring, a mixture of needle-like crystals and a flocculent solid is obtained. The solid is unsuitable for converting into a propylene polymerization catalyst.
  • the poured cone height of this material is 24.9 mm.
  • the particle properties were as follows : d 10 [ ⁇ m] 5.4 d 50 [ ⁇ m] 45.8 d 90 [ ⁇ m] 183.1 Span 3.88
  • Gas phase polymerizations are performed in a horizontal, cylindrical reactor measuring 10 cm in diameter and 30 cm in length with a volume of approximately one gallon (3.8 L).
  • the reactor is operated in a continuous fashion.
  • the reactor is equipped with an off-gas port for recycling reactor gas through a condenser and back through a recycle line to the nozzles in the reactor.
  • liquid propylene is used as a quench liquid.
  • the catalyst is introduced as a 0.5 to 1.5 wt% slurry in hexane through a liquid propylene-flushed catalyst addition nozzle.
  • a mixture of organosilane compound and trialkylaluminum in hexane are fed separately to the reactor through a different liquid propylene-flushed addition nozzle.
  • the Al/Mg molar ratio of 6 and the Al/Si molar ratio of 6 is used for all polymerizations.
  • polypropylene powder is passed over a weir and discharged through a powder discharge system.
  • the polymer bed in the reactor is agitated by paddles attached to a longitudinal shaft within the reactor that is rotated at about 50 rpm.
  • the reactor pressure is maintained at 300 psig (2.2 MPa).
  • Polymers with targeted melt flow rates are obtained by varying the amount of hydrogen in the reactor.
  • Gas composition in the system is monitored via an on-line process gas chromatograph.
  • Ethylene content in the reactor is adjusted by a mass-flow meter to vary the ethylene content in the final polymer.
  • Ethylene content in the gas composition is monitored via the same on-line process gas chromatograph.
  • the production rate is typically about 200 - 250 g/hour in order to maintain a stable process.
  • MGE catalyst support (10 g, example 3) is suspended in 200 mL of heptane and transferred under nitrogen to a 1-liter jacketed glass reactor fitted with an overhead stirrer.
  • the heptane is removed by decantation.
  • Toluene 125 mL is added and the slurry is stirred for 1 minute.
  • the stirrer is turned off and the solid is allowed to settle for 1 minute.
  • the toluene is removed by decantation.
  • 125 mL more of toluene is added, and the stirrer is started.
  • TiCl 4 105 mL, Akzo
  • TiCl 4 105 mL, Akzo
  • the reactor contents are warmed to 57 C and mixed for an additional 30 minutes.
  • the temperature is increased and as the temperature reached 100 C, 1.3 mL of di-n-butylphthalate (DNBP) is added and the reaction mixture stirred at 100 C for an additional 90 minutes.
  • DNBP di-n-butylphthalate
  • the stirrer is stopped and the liquid is removed by filtration through a small filter disk inserted into the slurry. After most of the liquid is removed, 125 mL of toluene and 105 mL of TiCl 4 are added and the slurry stirred at 100 C for 30 minutes. The stirrer is stopped, the solid is allowed to settle, and the liquid is removed through the filter disk. An additional 105 mL of TiCl 4 is added and the slurry stirred for 30 minutes at 100 C. The liquid is removed by filtration and 150 mL of heptane is added. The slurry is stirred at 57 C, the solid is then allowed to settle, and the heptane is removed.
  • the resulting solid had a uniform particle size and shape.
  • diisobutyldimethoxysilane as the organosilane compound, a 6.6 MFR random copolymer containing 3.2wt% ethylene is obtained.
  • the yield is 33,100 g PP/g catalyst, the copolymer powder had a bulk density of 0.40 g/cc, and there are low fines ( ⁇ 1% under 150 microns).
  • MGE catalyst support (example 4) is made in a similar manner as described in Example 3, except that some of the alcohol mixture is made up of recycled alcohol mixture from a previous support preparation. The support is converted to a catalyst in a similar manner as described in Example 5.
  • diisobutyldimethoxysilane as the organosilane compound, a 3.2 MFR polypropylene is obtained.
  • the yield is 24,500 g PP/g catalyst, the polymer powder had a bulk density of 0.46 g/cc, and there are low fines (1.1% under 150 microns).
  • the average particle size is 1150 microns and the span is 1.2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerization Catalysts (AREA)
EP16188726.0A 2003-11-04 2004-11-03 Particules sphériques Expired - Lifetime EP3141565B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10352138A DE10352138A1 (de) 2003-11-04 2003-11-04 Sphärische Partikel
EP04797531A EP1680454A1 (fr) 2003-11-04 2004-11-03 Particules spheriques
PCT/EP2004/012388 WO2005044873A1 (fr) 2003-11-04 2004-11-03 Particules spheriques

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
EP04797531A Division EP1680454A1 (fr) 2003-11-04 2004-11-03 Particules spheriques

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EP3141565A1 true EP3141565A1 (fr) 2017-03-15
EP3141565B1 EP3141565B1 (fr) 2021-03-17

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EP16188726.0A Expired - Lifetime EP3141565B1 (fr) 2003-11-04 2004-11-03 Particules sphériques
EP04797531A Ceased EP1680454A1 (fr) 2003-11-04 2004-11-03 Particules spheriques

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US (1) US7767772B2 (fr)
EP (2) EP3141565B1 (fr)
JP (1) JP4829118B2 (fr)
KR (1) KR20060130035A (fr)
CN (1) CN100535024C (fr)
BR (1) BRPI0416198B1 (fr)
DE (1) DE10352138A1 (fr)
WO (1) WO2005044873A1 (fr)

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MY156245A (en) 2008-04-25 2016-01-29 Reliance Ind Ltd Spheroidal particles for olefin polymerization catalyst
KR101140112B1 (ko) * 2009-05-22 2012-04-30 삼성토탈 주식회사 올레핀 중합 촉매용 디알콕시마그네슘 담체의 제조 방법, 이를 이용한 올레핀 중합 촉매의 제조 방법 및 이를 이용한 올레핀 중합 방법
SA3686B1 (ar) * 2009-10-16 2014-10-22 China Petroleum& Chemical Corp مكون حفاز لبلمرة الأولفين وحفاز يشتمل عليه
CN102762527A (zh) * 2010-02-25 2012-10-31 可儿康株式会社 混合二烷氧基镁粒状物、其合成方法及其利用方法
DE11806400T1 (de) * 2010-07-12 2014-01-23 Reliance Industries Ltd. Abriebfestes Katalysatorsystem zur Herstellung von Polyolefinen
WO2012034357A1 (fr) 2010-09-16 2012-03-22 中国石油化工股份有限公司 Support pour catalyseur de polymérisation d'oléfines, composant catalyseur solide et catalyseur
JP5854615B2 (ja) * 2011-02-18 2016-02-09 コルコート株式会社 混合マグネシウムジアルコキシド粒状物の合成方法およびその利用方法
CN102796208B (zh) * 2011-05-27 2014-08-06 中国石油化工股份有限公司 用于烯烃聚合的催化剂组分及其制备方法和用于烯烃聚合的催化剂以及烯烃聚合方法
MY169729A (en) 2011-06-28 2019-05-14 Reliance Industries Ltd Precursor for polyolefin catalyst
KR101786406B1 (ko) 2011-10-19 2017-10-17 닛뽕소다 가부시키가이샤 마그네슘알코올레이트의 제조 방법
US20150073108A1 (en) * 2011-12-21 2015-03-12 Reliance Industries Limited High surface area silicon derivative free magnesium- titanium catalyst system for ethylene polymerization and process of preparation thereof
EP2917247B1 (fr) * 2012-11-08 2023-12-20 Reliance Industries Limited Catalyseur ziegler-natta modifié pour la polymérisation du propylène
KR20170012387A (ko) 2014-05-22 2017-02-02 릴라이언스 인더스트리즈 리미티드 형상 제어된 전구 촉매 및 이의 제조를 위한 단일 포트 공정
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CN105801352B (zh) * 2016-04-18 2018-02-13 德州元光工贸有限公司 一种球形乙氧基镁的制备方法
CN105777490B (zh) * 2016-04-18 2018-02-13 德州元光工贸有限公司 一种大粒径乙氧基镁的制备方法
CN105801353B (zh) * 2016-04-18 2017-09-29 德州元光工贸有限公司 一种乙氧基镁的制备方法
EP3489244A1 (fr) 2017-11-28 2019-05-29 Scg Chemicals Co. Ltd. Composé de magnésium, son procédé de production et son utilisation
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CN114316102B (zh) * 2022-01-18 2023-12-22 北京吉海川科技发展有限公司 一种烷氧基镁载体、聚乙烯催化剂及其制备方法
JP2025538763A (ja) 2022-12-09 2025-11-28 イネオス ユーロープ アクチェンゲゼルシャフト 触媒成分

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EP0461268A1 (fr) * 1989-12-28 1991-12-18 Idemitsu Petrochemical Co. Ltd. Procede de production d'un constituant catalytique de polymerisation des olefines, et polyolefine
US5556820A (en) 1989-12-28 1996-09-17 Idemitsu Petrochemical Co., Ltd. Catalyst component for olefin polymerization and process for producing polyolefins
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US5965478A (en) 1995-02-13 1999-10-12 Toho Titanium Co., Ltd. Solid catalyst component and catalyst for polymerization of olefins
US20010012908A1 (en) 1999-12-15 2001-08-09 Idemitsu Petrochemical Co., Ltd. Magnesium compound, olefin polymerization catalyst, and method for producing olefin polymer

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JPH0374341A (ja) * 1989-08-16 1991-03-28 Korukooto Eng Kk 球形で粒度分布の狭いマグネシウムアルコラートの合成方法
EP0461268A1 (fr) * 1989-12-28 1991-12-18 Idemitsu Petrochemical Co. Ltd. Procede de production d'un constituant catalytique de polymerisation des olefines, et polyolefine
US5556820A (en) 1989-12-28 1996-09-17 Idemitsu Petrochemical Co., Ltd. Catalyst component for olefin polymerization and process for producing polyolefins
US5917100A (en) * 1993-01-07 1999-06-29 Clariant Gmbh Process for producing low molecular-weight poly-1-olefins
US5965478A (en) 1995-02-13 1999-10-12 Toho Titanium Co., Ltd. Solid catalyst component and catalyst for polymerization of olefins
US20010012908A1 (en) 1999-12-15 2001-08-09 Idemitsu Petrochemical Co., Ltd. Magnesium compound, olefin polymerization catalyst, and method for producing olefin polymer

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CN100535024C (zh) 2009-09-02
DE10352138A1 (de) 2005-06-16
JP4829118B2 (ja) 2011-12-07
US7767772B2 (en) 2010-08-03
CN1875038A (zh) 2006-12-06
JP2007509901A (ja) 2007-04-19
EP1680454A1 (fr) 2006-07-19
BRPI0416198B1 (pt) 2015-08-18
US20080262178A1 (en) 2008-10-23
EP3141565B1 (fr) 2021-03-17
KR20060130035A (ko) 2006-12-18
WO2005044873A1 (fr) 2005-05-19

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